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Book Review High Resolution NMR in the Solid State. Fundamentals of CPMAS. By E. O. Stejskal and J. D. Memory

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BOOKS
Auf der Heyde on transition metal complexes is very well written and gives the
reader a good perspective how to use
statistical methods to extract order from
(greatly simplified) clusters of data. Cluster analysis and principle coordinate analysis are techniques to which the average
chemist is exposed; however, Auf der
Heyde does an excellent job showing the
usefulness of such methods in studies of
ligand field exchanges and rearrangements. The final chapter of Volume 1 by
Schweizer on conformational analysis is
also a classic in the field. The conformational analysis of polyaryl X compounds
and medium ring systems is one of the
proving grounds for structure correlation
analysis. Schweizer clearly presents these
classic studies.
3) Crysstul Packing: Part 3 comprises
three chapters which really display the
power of structural correlation theory to
elucidate molecular interactions when
linked to a database like that of CCDB.
The chapter by Brown builds directly on
Pauling’s fundamental work; this chapter
demonstrates how elegantly the Pauling’s
bond-lengthlbond-order relationship applies to a wide variety of systems. Indeed,
this is really the basis of the original structural correlation ideas. The following
chapter, by Bernstein, Etter, and Leiserowitz, on hydrogen bonding is one of the
best in the collection. Although I found
their original definition for the existence
of a hydrogen bond to be cyclic (a hydrogen bond exists when there is evidence for
the existence of a bond involving a hydrogen atom) they present a practical scheme
for describing and organizing hydrogen
bonding patterns as well as a number of
useful energetic thumb rules for predicting the hierarchy of hydrogen-bonded
aggregates. This chapter would be improved if standard chemical structural
formula accompanied the many packing
diagrams which contain no atomic or
bonding labels, and it would be nice if
they consistently used their network notation to annotate all of the exemplary figures. Figure 1 1.15 on page 459 has the labels for part a and part b reversed. The
chapter by Gavzzoti describes the substantial advances that have been made
toward the derivation of a consistent force
field for crystal environments. This chapter is perhaps one of the most important
for future developments in computational
crystal engineering. The formulae in the
chapter often used the same capital letters
to mean different things which makes
the reading a little bit cumbersome, but
the ideas are well worth the effort.
Table 12.2 must have some numbers for F
switched or wrong, particularly those for
tetraphenylmethane, adamantane, and
DABCO.
4) Proteins and Nucleic Acids: Part 4
contains a series of chapters on biological
structure, which except for Chapter 13 by
Klebe d o not fully blend into the style of
the book. The chapter on steroids is more
an expose than a lesson. The chapter of
protein structural motifs is not easily accessible to the nonspecialist; this chapter
could have been a jewel with a few more
pages of background, and a conscientious
attempt to define terms and jargon rather
than just citing literature and expecting
the readers to fend themselves. Blundell’s
contribution was for me interesting but of
such small scope that I felt it might well
have been included with a broader discussion. Indeed, a combined chapter containing the principles of Chapters 15, 16, and
17 from a generalist’s perspective would
have been more fitting for the book. Ultimately, although this final section of four
chapters is competent. it reads like an afterthought rather than an integral part of
the structural correlation field.
In summary, I feel all of the contributing authors did a splendid job; however,
the diversity of topics is such that few
readers will remain “riveted” throughout
the whole 18 chapters. Indeed, in this day
of interdisciplinary hype. it is a pleasure
finally to read a book that truly captures
the spirit of boundary-free research. Thus,
I would call “Structure Correlation” by
Burgi and Dunitz a “must have” for anyone interested in molecular structure. My
copy stands on my shelf of most accessed
books.
Jay S. Siege1
Department of Chemistry
University of California-San Diego
La Jolla. CA (USA)
High Resolution NMR in the Solid
State. Fundamentals of CP/MAS. By
E. 0. Stejskal and J. D. Memory. Oxford University Press, Oxford, 1994.
189 pp., hardcover E 30.00.-ISBN
0-19-507380-0
The subject of high-resolution solidstate NMR, including all fundamental
aspects of N M R of solids, has been thoroughly treated in several excellent monographs. However, these books have been
written by physicists in language which is
often not at all familiar to chemists. At the
other extreme, a number of Fairly oversimplified, purely qualitative introductions to solid-state N M R have appeared,
aiming at the chemists’ approach by try-
ing to more or less completely avoid
“unloved” topics such as mathematics
and quantum mechanics. In between these
two extremes there exists a large gap: the
attempt to provide a bridge between these
two worlds is, by its very nature. an extremely difficult task, like trying to square
the circle. The task is so difficult because
there simply is no purely qualitative approach to high-resolution solid-state
N M R which would d o justice to the subject. This difficulty of translating and
communicating between the worlds of
physics and chemistry is almost certainly
the reason why no such “intermediate”
textbooks on CP/MAS N M R have appeared on the otherwise well supplied
N M R book market. On the other hand, a
textbook on CP/MAS N M R at that level
would certainly represent a much needed
commodity, especially since many Fascinating and challenging applications of
high-resolution solid-state N M R methodology in the field of chemistry remain to
be explored. Any serious effort to make
the principles of CP/MAS N M R more
accessible to the chemistry community is
therefore to be welcomed.
The book by Steijskal and Memory represents a quite successful attempt at
squaring the circle. From every page in
this book it is obvious that it has resulted
from long experience of teaching the subject to undergraduate and graduate students. The strategy follows a step-by-step
method, starting with the introduction of
the basic principles of N M R in Chapter 1.
This introduction also includes a brief explanation of the density matrix formalism
which is absolutely necessary. This explanation should certainly provide a golden
bridge for readers more familiar with solution-state N M R ; the example chosen is
the polarization transfer experiment in solution using the DEPT sequence. Naturally, an introduction compressed into approximately ten printed pages can only
outline the general idea, but all important
references for further reading are given.
Chapter 2 is devoted to cross-polarization (CP) in the solid state and follows
“traditional” descriptions within the
framework of a thermodynamic approach, introducing the concept of spin
temperature. For this chapter too all important key references are given in the
bibliography. Although it is implicitly
clear that this approach to explaining C P
under Hartmann-Hahn matching conditions is only valid for a rigid lattice with
an abundant spin reservoir as the source
of magnetization. a more explicit statement about the limitations of the thermodynamic approach would seem necessary.
Also, given the strategy of starting out
BOOKS
from a familiar solution-state polarization transfer experiment in Chapter 1 , a
mention of Hartmann-Hahn C P in solution via J-coupling would probably have
helped the reader to appreciate the unified
picture of gradual changes of NMR behavior all the way from non-viscous liquids t o rigid solids.
Chapters 3 and 4 deal with spin-spin
interactions and with magic angle spinning (MAS). including a very brief encounter with average Hamiltonian theory.
Again. this iz a topic of fundamental importance for the understanding of MAS
spectra. and for a more thorough understanding the reader will need to refer to
the original literature. Finally, Chapter 5
is concerned with spectrometer and probe
design. I t is probably a matter of taste
whether one considers such technicalities
as an important aspect of the fundamentals of C P MAS. Personally I would tend
t o agree with thc authors that such a chapter should be included: tuned rf circuits
:ind the principles of construction of
double resonance probes are of vital practical importance. A short description of
the basic features may, therefore, help to
bridge yet another gap. I feel that this
chapter will help to improve communication between "users" and engineers and
technicians. The collected appendices at
the end of the book are too short to be
useful.
In summary. I can recommend this
book ;is a useful, solid guide to the
"secrets" o f CP, MAS for all readers who
would tend to be frightened by physics
monographs. but nevertheless want a
deeper understanding than merely being
able to extract a n isotropic chemical shift
from a CP,MAS spectrum. Armed with
this book. with the desire to uti~lerstand,
and with access to the library (for the literature cited in the bibliographies), every
chemist should be able to master the basics
of high-resolution solid-state NMR.
Angelikn Sehold
Bayerisches Geoinstitut
UniversitSt Bayreuth
Bxyreuth (Germany)
The Chemistry of Organophosphorus
Compounds. Volume 3. Phosphonium
Salts, Ylides and Phosphoranes. (Series: The Chemistry of Functional
Groups. Series editor: S. Patui.)
Edited by E R. Hartlej.. Wiley,
Chichester, 1994. 442 pp., hardcover
E 120.00.--ISBN 0-471-93057-1
Volumes 1 and 2 of this four-volume series on the chemistry of organophosphorus compounds appeared in 1990 and
1992; the third volume has now been published. A survey of this nature covering
the still rapidly advancing field of
organophosphorus chemistry is very welcome, especially since other works in this
area, such as the handbook edited by
G. M. Kosolapoff and L. Maier, are now
over twenty years old.
It was noted earlier in reviews of the
two previous volumes (Angrit..Chenz. I t i f .
E d Engl. 1991. 30, 1046; ibict. 1993. 3-7,
1215) that a clear plan for the work as a
whole did not seem to emerge. This third
volume does little to alter that view, but it
is at least internally consistent. It covers
the phosphonium ylides and phosphonium salts, together with the closely related
phosphoranes containing a five-coordinated pentacovalent phosphorus atom.
The final chapter ("Chemical Analysis of
Organophosphorus Compounds", by H.
Feilchenfeld) does not really fit into the
context of the rest of the volume, and is
not directly related to the preceding chapters. It is in itself a very welcome contribution. but would perhaps have been better
placed a t the beginning of the series, or
alternatively it could have been delayed
until the last volume.
The book contains six contributions altogether on the ylides and phosphoranes.
all written by recognized experts in their
fields. Chapter I (D. G. Gilheaney) and
Chapter4 (S. M. Bachrach and C. I .
Nitsche) are concerned with bonding and
structure in phosphonium ylides, phosphonium salts, and phosphoranes. These
two fundamental chapters deal with similar subjects. but differ in their lengths and
in the depth of the treatment. A certain
degree of overlapping is evident.
The longest chapters are those concerned with the preparation, properties.
and reactions of phosphoniuin salts
(Ch. 2, H. J. Cristau and F. Plenat) and
with phosphoranes (Ch. 3. R. Burgada
and R. Setton). Chapter 5 (K. S. V. Santhanam) deals with the electrochemistry
of ylides, phosphonium salts, and phosphoranes. and Chapter 6 ( M . Dankowski)
with the photochemistry of these classes
of compounds.
Concluding the book. Chapter7 describes the chemical analysis of
organophosphorus compounds. giving an
overview of the available methods. froin
the classical wet-chemicnl methods to the
various instrumental methods (gas chromatography, mass spectrometry. etc.).
The very important method of NMR
spectroscopy, especially the application of
3'P N M R methodology to phosphorus
compounds, is not included (although it is
true that this has recently been covered by
other authors). Chapter 7 alone contains
over 400 literature references.
The book provides a detailed coverage
of the field of phosphonium ylides. phosphonium salts, and phosphoranes in
about 350 pages of closely printed text.
For each of these classes of compounds
several hundred well-chosen references
are listed (original papers. review articles,
and monographs). giving the reader easy
access to the literature. However. only a
few of these refer to publications from
1990 onwards. Also there are many instances where insufficient care has been
taken with the references. I t is disconcerting when the same author's name appears
with two, or even three. different
spellings, and these garbled names then
reappear in the author index. sometimes
immediately adjacent to each other and
sometimes widely separated.
Despite some shortcomings of the kind
mentioned above. this third volume in the
series edited by Hartley i h a n indispensable addition to the literature for all
organophosphorus chemists. and the final
volume is awaited with interest. Finally,
this review would be incomplete without a
comment which unfortunately nowadays
applies all too often. namely that although the book should be in the departmental library of every organophosphorus chemist. its high price is likely to
discourage any wider circulation.
Rcitihri~~l
Scliniirtrler
Institut fur Anorganische und
Anal) iische Chemie
der Technischcn Universitlit
Braunschweig (Germany)
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